New vinyl compounds and methods for their preparation



United States Patent 3,100,217 NEW VINYL CUWOUNDS AND METHQDS FGR THEM PREPARATION Bode K. W. Bartocha, 4567 Main St, Riverside, Calif. No Drawing. Filed Mar. 31, 1959, Ser. No. 803,333 2 Claims. (Cl. 260-448) (Granted under Title 35, US. Code (1952), sec. 266) The invent-ion herein described may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This invention relates to new vinylated compounds of the type formula (CI-I CI-D PJR wherein R is an element selected from the class consisting of B, Al, Ga and Ge, R is halogen, alkoxy or aroxy, and x and y are whole numbers from 1 to 2 such that their sum is 3. The compounds include monoand di-vinylated compounds containing m element from the class consisting of B, Al, Ga and Ge, and a halogen atom or other functional group, such as, alkoxy or aroxy. Typical monovinylated and di-vinylated compounds are vinylaluminum dichloride and divinylaluminum chloride, respectively. The mono-vinylated compounds are made by reacting divinylmercury, divinylzinc, tetravinyllead or tetravinyltin with halogen, alkoxy or aroxy derivatives of elements from the above class.

Prior to this invention it has not been possible to make the monovinylated and/or di-vinylated compounds by a one-step method which could be controlled. The use of the di-vinyl and tetravinyl starting materials mentioned above makes it.- possible to produce both type compounds by a controllable process which is economical and produces excellent yields of from 75% to 95%. The divinylated compounds of the invention can only be produced by using the tetravinyl starting materials, however, the monovinylated compounds can also be produced from the tetravinyl starting materials.

The invention is illustrated by the following examples which are exemplary only of the invention but in no way limiting thereof. In the examples the vinyl radical is represented by the symbol Vi. Stoichiometric amounts were used in all examples. Examples 19, inclusive, .illusirate the preparation of the monovinyl derivatives.

Example I ViBF was prepared according to the reaction equation Vi Hg+BF ViBF +ViHgCl by condensing BF onto Vi l-lg in a high vacuum system at 196 C. The mixture was allowed to warm up to room temperature where reaction takes place instantly.

The ViBF a gas (V.P. 75 mm. at 780 C.), may then be removed by standard techniques.

Example 11 ViBCl was prepared according to the reaction equation Vi Sn+BCl e ViBCl +Vi SnCl by mixing ViSn and BCl in Nujol at 0 C. The mixture was then allowed to Warm up to room temperature and stirred for eight hours. Upon purification of the reaction product a pure fraction of V-iBCl was obtained boiling at 45.5 C./ 760 mm. Hg. (Nujol is a white mineral oil having a boiling range 180-280" C.)

Example 111 ViAlCl was prepared according to the reaction equation Vi Zn+AlCl ViAlCl +ViZnCl in reacting Vi Zn and AlCl in Nujol by stirring the 3,100,217 Patented Aug. 6, 1863 "Ice reactants at 0 C. eight hours. The liquid fraction, ViAilCl was then removed by vacuum distillation. It had a boiling point of 5558 C./4 mm. Hg.

Example IV ViGaCl was prepared according to the reaction equation Vi Zn+GaCl ViGaCl +ViZnCl by stirring Vi Zn with an excess (10%) of GaCl for-five hours at 0 C. During purification the isolated ViGaCl polymerized. Analysis of the polymer confirmed the formula of the compound.

Example V ViSiCl was prepared according to the reaction equation Vi Hg+SiCl +ViSiOl +ViHgC1 by heating a mixture of Vi I-Ig and SiCl to 60 C. for six hours. The volatile material was removed in vacuo and then fractionated by distillation. The formed ViSiCl had a boiling point of 92 C./760 mm. Hg.

Example VI ViGeCl was prepared according to the reaction equation Vi Hg+GeCl ViGeCl +ViHgCl by refluxing Vi l-lg and GeCL, at -85" for live hours. The volatile material was removed in vacuo and then fractionated by distillation. The ViGeCl had a boiling point of l28.5 C./760 mm. Hg.

tionated by distillation. The formedViPCl had a boiling point of 104 C./760 mm. Hg.

Example IX ViAsCl was prepared according to the reaction equation Vi S-n+AcCl ViAsCl +Vi SnCl by heating Vi Sn and AsCl to 80 C. for six hours. By fractionated distillation a portion of material was .obtained boiling at 60-61" 0/40 mm. Hg. Analysis'confirmed the compound as ViAsCl The following examples illustrate the preparation ,of the diviny-l derivatives.

Example X Vi AlCl was prepared according to the reaction'equation as follows. Vi Pb and AlCl were allowed to react in an inert solvent at a temperature of about 0 C. while stirring for eight hours. The volatile material, VigAlCl, was then removed and purified further by high'vacuum techniques. The formed Vi AlCl had a boiling point of 60-65 C./4 mm. Hg.

3 Example XI Vi PCl was prepared according to tion Vi Pb+PCl Vi PC1+Vi PbCl by heating Vi Pb and PCl under nitrogen at 86 C. for about eight hours, removing the volatile part in vacuo and then fractionating itby distillation. The formed Vi PCl had a boiling point of Ill-112 C./ 760 mm. Hg.

Example XIII Vl ASBI was prepared according to the reaction equation the reaction equaby heating Vi Sn and AsBr to 75 C. for six hours. Upon purification of the reaction product- VI'ZASBT, boiling at 7375 C./ 14 mm. Hg, was obtained.

All of the above compounds of the invention were identified by standard analysis procedures including infrared and elemental analysis.

The compounds of the invention have utility as polymerization agents and as intermediates for the formation of high temperature polymers. Their co-hydrolysis prodnets with organosilicon or organotitanium compounds are high temperature polymers. For example, the co-hydrolysis product of vinyl aluminum dichloride with diphenyl silicon dichloride may by conventional hydrolysis procedures is a useful high temperature dielectric. The compounds are also useful as polymerization catalysts and accelerators. For example, they are useful as catalysts in the manufacture of polyethylene and polypropylene. They can be substituted for conventional reaction accel erators in the production of organovinyl polymers, such as, polyvinyl chloride or polyvinyl tetrafluori'de.

As the compounds of Vi I-Ig, Vi Zu, Vi Sn and Vi Pb are new compounds, a method for the preparation'of each is given below.

Divinylzinc was prepared as follows: A slurry of zinc chloride (0.425 mole in 300 ml. tetrahydrofuran) was added slowly to vinylmagnesium bromide (1 mole in 450 ml. tetrahydrofuran) cooled to C. The mixture was then maintained at 55 for twelve hours, after which time it was cooled to C. and 250 ml. of dc-gassed diethyl ether was added. The supernatant liquid was then filtered under prepurified nitrogen through glass wool into a receiver. Experience showed that while div-inylzino is fairly stable in dilute solution it becomes much less stable in concentrated solutions, particularly in the presence of salts. Therefore, after the vinylation step all subsequent manipulations should be done as rapidly as possible. Solvent was removed by pumping at room temperature until the volume of liquid was reduced to about 100 ml. The residue was then vacuumtransferred into a 150 ml. distillation flask cooled to --78 C., at which temperature it was crystalline, and then distilled, first at 200 mm. pressure to remove the last traces of tetrahydrofuran, and subsequently at 32/22 mm. The divinylzinc obtained (6 g. yield 10% based on the zinc chloride taken for reaction) was tensimetrically homogeneous. In other preparations of diviinylzlnc the yields varied but were rarely greater than 25%.

Diviuylmercury was prepared by treating an excess of vinylmagnesium bromide with mercury (II) chloride in tetrahydrofuran. Two moles of vinylmagnesium bromide were prepared under a prepur-ificd nitrogen atmosphere in 600 ml. of tetrahydrofuran, which had previously been distilled from lithium aluminum hydride to remove water and peroxides. After formation of the Grignard was completed, mercury (H) chloride (0.77 mole in 250 ml. tetrahydrofuran) was added slowly with vigorous stirring, the reaction flask being cooled with ice water. When the mercury (11) chloride had been added, the reaction mixture was maintained with stirring at a temperature of about 55 C. for 12 hours. The flask was then cooled to room temperature, and the excess of Grignard was hydrolyzed with approximately 250 ml. of a saturated ammonium chloride solution. The organic layer was decanted into a distillation flask, and the residual salts washed with several portions of :diethyl ether, the washings being added to the flask. Most of the solvent was then distilled off at normal pressure. Paraliin oil was added as a carrier, and distillation was continued under reduced pressure. In ths way, at- 59.5 C. and 20 mm, 167 g. (yield 85.10%) of the new compound divinylmercury were obtained. (Found: C, 19.1; H, 2.8; Hg, 78.0. C H Hg required: C, 18.7; H, 2.4; Hg, 78.9%.)

Tetravinyllead is made as follows: Sixty-six g. (0.5 mole) of vinylmagnesium bromide was prepared under a nitrogen atmosphere in 500 ml. tctrahydrofuran, freshly distilled from lithium aluminum hydride. After formation of the Grignard was accomplished, 49.8 g. (0.1 mole) of potassium hexachloroplumbate was slowly added while stirring, the reaction flask being cooled with ice water. The KgPbclg was prepared by chlorinating an ice-cold solution of PbCl (0.2 mole) in concentrated hydrochloric acid (300 ml.). After all the PbC l had reacted,

perature of 55 C. for eight hours.

.. freshly distilled tetrahydrofuran.

'a saturated solution of KCl was added to precipitate the K PbCl It was washed wth ice-cold ethanol. Yield 85%. When all of the K PbCl had been added, the reaction mixture was maintained with stirring at a tem- The fiask was then cooled to room temperature and the excess of Grignard was hydrolyzed with approximately ml. of saturated aqueous solution of ammonium chloride. The brown organic layer was decanted into a distillation flask and the residual salts washed with severl portions of fresh tetrahydrofuran, the washings being added to the main portion. Most of the solvent was then removed at normal pressure. Parafiin oil Was added as a carrier and distillation was continued under reduced pressure. In this way, at 5254 C. and 4 mm. Hg, 21.9 g. (69.5%) of the new compound tetravinyllead were obtained.

Tetravinyltin was made as follows: 266.3 g. (2.5 moles of vinylrnagnesium bromide were prepared in 1000 cc. of The reaction was carried out in a 2-liter, 3-necked flask, fitted with a reflux condenser, mechanical stirrer and a dropping funnel. After formation of the Grignard was completed 130.3 g. (0.5 mole) of tintetrachloride was added dropwise and the mixture then refluxed for eight hours. On cooling the reaction mixture was hydrolyzed with approximately 285 cc. of an aqueous solution of saturated ammonium chloride. The organic layer was separated, the solvent removed and the residue carefully fractionally distilled under reduced pressure at 55-57 C./ 17 mm. Hg, to yield 98 g. of tetravinyltin.

Other reactants than the halogen compounds of elements of groups III, IV and V of the periodic table may be used. Other equivalents for these functional groups which may be used are the alkoxy and aroxy groups. Alkoxy groups which may be used are -OCH OC H OC H Aroxy compounds which are suitable reactauts are The inventionhas been illustrated using compounds in which the unsaturated organic radical is the vinyl group, however, analogous compounds in which the vinyl group is replaced by other unsaturated radicals, such as, propylene, butylene and higher unsaturated radicals, may be used in the process to produce analogous products.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed is:

1. The process for preparing vinylaluminum dichloride which comprises reacting one molar equivalent of divinylzinc with one molar equivalent of aluminum triohloride at 0 C. for eight hours.

2. The process for preparing divinyl-alurninum chloride which comprises reacting one molar equivalent of tetravinyllead with one molar equivalent of aluminum trichloride at 0 C. for eight hours.

References Cited in the file of this patent UNITED STATES PATENTS Ramsden Jan. 19, 1960 Willie Jan. 10, 1961 Ramsden Nov. 28, 1961 OTHER REFERENCES Chemical Society Proceedings, April 1958, page 116 Chem. Soc. 79 (1957), pages 515, and

claim.

European Scientific Not-es, July 1, 1952(vol. 6. No. 113),

page 178. London.

Published by Office of Naval Research, 

1. THE PROCESS FOR PREPARING VINYLAUMINUM DICHLORIDE WHICH COMPRISES REACTING ONE MOLAR EQUIVALENT OF DIVINYLZINC WITH ONE MOLAR EQUIVALENT OF ALUMINUM TRICHLORIDE AT 0*C. FOR EIGHT HOURS.
 2. THE PROCESS FOR PREPARING DIVINYLALUMINUM CHLORIDE WHICH COMPRISES REACTING ONE MOLAR EQUIVALENT OF TETRAVINYLLEAD WITH ONE MOLAR EQUIVALENT OF ALUMINUM TRICHLORIDE AT 0*C. FOR EIGHT HOURS. 